Azides are the precursors of two important derivatives in synthetic organic chemistry. Achiral amines are not as demandable as that of chiral ones. Chiral amines and diamines have versatile uses in enantioselective reactions. Both simple and amino alcohols were undergone smooth azidation reaction in the mixture of NaN3, H2SO4 in toluene solvent and afforded good to charming yields. Importantly, optical purity of some chiral amino alcohols was reserved during azidation reaction. This is an efficient method to synthesise new azides for the fabrication of new organocatalyst which is friendly to the environment.